Sulphated acyloins and process of producing them



Patented Sept. 26, 393% s'raras PATENT OFFICE SULPHATED ACYLOINS AINDPROCESS OF PRODUCING THEM Clyde-0. Henke, Wilmington, Del., and JosephL. Richmond, Woodstown, N. J., assignors to E. I. du Pont de Nemours &(Jompany, Wilmington, Del, a corporation of Delaware No Drawing.Application December 13, 1937, Serial No. 179.618

8 claims. (on. zoo-s) This invention relates to sulphated chemicalcompounds, their'preparation, and'use. Particularly it relates tosulphation products of acyloins, their preparation and applications aswetting, dispersing, deterging and emulsifying agents, as

.dye bath assistants and in general as textileassistants.

Applicants are aware that sulphated alcohols are old in the chemicalart, but it is believed that acyloins with theirparticular'configuration and properties have not been sulphatedheretofore. On being sulphated acyloins may react in accordance witheither of two tautomeric structures, the keto-alcoholic structure or thedl-enolic structure on on Consequently a sulphate ester may possesseither of the following structures or both 0 0803MB OH OSOaMo n-zi-hn-nen o= '41 Also, the acyloins may be disulphated, in which case itis thought that the product has the second configuration Developments inthe textile industry have,

created a demand for improved agents of the class generally referred toas textile assistants. It, therefore, is the general object of thisinvention to provide a new and useful group of such materials, andprocedure for their manufacture; further objects will be evident fromthe description of the invention.

It has been discovered that a new group of chemical compounds ofparticular use in the textile arts can be obtained by subjectingacyloins to the action of mild sulphating agents to produce the mono anddi-sulphate esters.

Acyloins themselves may be prepared conven iently by the procedure of U.S. Patent 1,996,471 of April 2, 1935. That process consists in reducingan aliphatic acid ester or a mixture of such esters in xylene by meansof a suspension of finely divided sodium in xylene. The sodiumderivative of the dienol is decomposed with acid and the resultingacyloin is separated from the xylene by fractional crystallization. Thefollowing equations in which methyl acetate is the starting ma,-

terial' are taken from U. S. Patent 1,996,471. They are given in thepatent as typically illustrative of the steps in known procedure forpreparation of acyloins.

Another description of the preparation of acyloins may be found on page2303, vol. 57, of the 1 Journal of the American ,Chemical Society.

The citations are given merely for informative purposes and it is to beunderstood that applicants" sulphation process applies to acyloinsmatter how obtained.

In'the sulphation of acyloins a wide range of sulphat ing agents may beused but it is preferred to employ chlor-sulphonic acid orchlorsulphonic acid with ether or other suitable diluent. Con-'centrated sulphuric acid modified with commonly used inhibitors, such aspotassium acid sulphate gives good results. Among other particularsulphating agents that may be mentioned as satis factory for ourpurposes are:

in the sulphating acid it is possible to operate at 45 somewhat highertemperatures and shorten the time of sulphation.

The following examples, which are not to be construed as limitative,illustrate the sulphation of particular acyloins by procedure within thescope of the invention: I

Example I To 30 grams of capryloin (prepared by the sodium reduction ofmethyl caprylate) in 100 cc. of

anhydrous ether was added a solution of 15 grams chlorsulphonic acid(110% excess of calculated quantity necessary for mono sulphation) in 15cc. of anhydrous ether. The acid solution was gradually added over aperiod of 30 minutes, the temperature being maintained at -13", by meansof an ice bath. When the acid had all been added, the sulphation masswas stirred one-half hour longer, then neutralized in a mixture of 200cc. of ice and 25 grams 50% caustic soda solution.

The solution was evaporated to dryness and the sulphate ester extractedwith methanol. The methanol solution was diluted with water, ex-

tracted twice with petroleum ether and the extracted solution evaporatedto dryness on the steam bath under moderate vacuum. The monosulphationproduct was'a white solid, soluble in water with foaming. It possessedexcellent wetting-out properties.

Example H .To 20 grams of caproin, prepared by the sodium reduction ofmethyl caprate (CH3O0C10H19) in 100 cc. of anhydrous ether was added asolution of 8.5 grams of chlorsulphonic acid in 10 cc. of anhydrousether. The solution was stirred one half hour during which time theoriginally cloudy solution cleared. The sulphation mass was poured into200 ,cc. of ice and neutralized to pink with phenolphthalene with 10%caustic soda. The solution was evaporated, the solid taken up inmethanol diluted with water, purified by petroleum ether extraction, andthe solution evaporated to dryness. The product was the mono sulphationproduct of caproin. It dissolved in water to give a solution whichfoamed.

Example III To 20 grams of capryloin in 100 cc. of anhydrous ether wereadded 20 grams of chlorsulphonic acid. The acid was added over aperiodof 30 minutes and then stirred for an additional 30 minutes. Thesulphation mass was neu tralized by drowning in an ice-caustic sodasolution. The solution was evaporated to dryness, taken up in methanoland purified as in the preceding examples. The product is thought to bethe di-sulphation product of capryloin.

Example IV orated to dryness and extracted with methanol. I

The methanol solution which contained the sulphated acyloin was dilutedwith water, the unsulphated acyloin extracted with petroleum ether, andthe methanol-water solution evaporated to dryness. A yellow waxy producthaving wetting out properties was obtained.

Example V 30 grams of mixed acyloins prepared as in Example IV butcontaining an average of sixteen carbon atoms were sulphated and treatedas in Example I. The product was foundto have excellent wettingproperties.

I lithium, magnesium,

Emmple VI 30 grams of mixed acyloins prepared by reducing the esters ofmono-carboxylic fatty acids derived from the oxidation of oleic acidwere sulphated and treated as in Example IV. The prodnot obtained was awaxy solid with good wettin power.

While the examples relate to comparatively few starting materials manyother straight chain acyloins can be used such as acetoin, butyroin,valeroin, myristoin, lauroin; mixed acyloins as acet-lauroin from methylacetate and methyl laurate, butyrcaproin from methyl butyrate and methylcaprate, acyloins of mixtures of acids as coconut oil acids, lard oilacids, rape seed oil acids; branched chain acyloins as iso butyroin, isobutyrlauroin from methyl iso butyrate and methyl laurate; unsaturatedacyloins as oleoin butyr-oleoin from butyric and oleic methyl laurate;unsaturated acyloins as oleoin butyroleoin from butyric and aleic methylesters. Also acyloins from cyclic acids such as the naphthenic acids.phenyl acetic acid and phenyl butyric acid can be used.

In foregoing examples sodium salts of sulphated acyloins have beendisclosed but salts of other bases can be used, such as those oipotassium,

ammonium, trimethylamine, triethanolamine and pyridine. For certainpurposes it may be necessary or at least advantageous to use a saltother than the sodium salt. Of course, the free acid can be used whendesirable. 1

The acyloin sulphation products comprise a new class of compounds whichare water soluble and are highly useful in the textile and otherindustries. By using different acyloins and degrees of sulphation thepropertiesv of the sulphate esters can'be greatly varied. The loweracyloin sulphation products e. g. acetoin sulphate, butyroin sulphate,and isohexion sulphate are good printing paste assistants andmercerizing assistants; the sulphation products from higher acyloins i.e. containing a radical of eight or more carbon atoms such as capryloin,acetoleoin, acet-myristoin serve well as wetting agents; sulphationproducts of coconut oil acid acyloins, butyr-stearoin, caprolauroin makegood detergents. Sulphation products from stearoin and myristoin areuseful as dry cleaning soaps. Acyloin sulphation products can also bevused in making emulsions of the oil in water type, in making edibleemulsions, and as wetting and spreading agents for insecticides andfungicides. They can be used in solid form or as aqueous solutions aloneor mixed with other materials such as sodium carbonate, borax, sodiumsilicate, etc. In the following listings there are shown specificallymany further uses in which various sulphated acyloins can be employedwidth benefit.

A. Treatment for the processing and improvement of natural or synthetictextile materials involving:

1. Cleansing vegetable and animal fibers when removing fatty or oilymaterials.

2. Carbonization.

3. As an addition to flax wetting baths.

4. Falling.

5. Sizing.

6. As an addition when sizing is removed from textile materials.

7. Impregnating. .8. Bleaching.

9. Mordanting.

10. As an addition to soap in an acid or hard water bath.

Mercerizing lye liquors. v 12. Improvement of absorption capability offibrous materials particularly when sub jected to a treatment forfinishing, softening, stiffening, coloring or special chemical treatmentsuch as waterproofing or mildew-proofing. Delustering or lustering.Degumming. Kier boiling. scouring. Stripping. Felting. '19. Oiling orlubricating.

20. Weighting or loading. B. Dyeing processes:

. Dyeing in neutral, acid or alkalinebaths. Reserving cotton in acidbaths. Dyeing with developed dyes. Dyeing of animal fibers with vatdyes. Dyeing cellulose acetate fibers with insoluble dyes. Dyeing andprinting with aniline black.

7. Dyeing of leather.

8. In printing pastes to assist in the dispersion of the dye or dyecomponentand in the penetration into the natural or synthetic fiber.

C. Dyes and coloring: 1. For making pastes of dyes or dye components.

2. For the production of pigments of azo,

basic acid vat, and sulphur dyes in a finely divided condition.

ganic pigments.

D. Mscellaneous uses:

1. For converting liquid or solid substances normally insoluble inwater, such as hydrocarbons, higher alcohols, other omgen containingcompounds, fats, oils, waxes, resins, pitches and pitchy substances intoclear solutions or stable emulsions or dispersions.

2. As cleansing agents particularly in hard water and where a fatty oroily film resists the ordinary cleansingmedia.

tanning.

. In softening'and treating baths for hides and skins, particularly thefat liquor treatment.

5. In flotation processes including minerals and oils such as therecovery of fixed oil from the oil sands.

. In tooth pastes, tooth powders and dentifrices generally.

losic materials generally.

. In the treatment of paper pulp and cellu- E; General:

1. The reagents may be used in pure or standardized form. i 2. They maybe used in conjunction with the known processingor treating agents.

As many apparently widely difierent embodi-' ments of this invention maybe made without departing from the spirit and scope thereof, it-

is to be understood that we do not limit ourselves to specificembodiments thereof except as defined in the appended'claim's.

We claim:

1. The'process of preparing surface active substances which comprisesreacting acyloins with a sulphating agent at a temperature in theneighborhood of C. until sulphation is at least partially. complete.

2. 'The process of preparing surface active substances which comprisesreacting acyloins dissolved in an inert organic solve t with asulphating agent at a temperature in he neighborhood of 0 C. untilsulphation is at least partially complete. v

3. The process of preparing surface active substances which comprisesreacting acyloins dissolved in an inert organic solvent with chlor- 8.In latex solutions and adhesives contain-' sulphonic acid dissolved inan inertsolvent at a of 0 C. until sulphationls at least partiallycomplete, neutralizing the reaction mixture, and separating thesulphated product by extraction with separating'the sulphated product byextraction with a solvent.

6. sulphated acyloins. 7. sulphated capryloin.

- 8; New products useful as textile assistants included in the groupconsisting of sulphated acyloins and water-soluble organic and inorganicsalts thereof.

CLYDE O. EENKE. JOSIEE'H L. RICHMOND.

